Method of preparing non-migratory color couplers for yellow



United States Patent 3,138,604 METHOD OF PREPARING NON-MIGRATORY COLOR COUPLERS FOR YELLOW Arthur Henri De Cat, Mortsel-Antwerp, Raphael Karel Van Poucke, Mechlin, and Marcel Hendrik Verbrugghe, Wilriik-Antwerp, Belgium, assignors to 'Gcvaert Photo- Producten N.V., Mortsel-Antwerp, Belgium, :1 Belgian company No Drawing. Filed Oct.- 31, 1960, Ser. No. 65,882 Claims priority, application Germany May 19, 1960 1 Claim. (Cl. 260-294.8)

The present invention relates to a method of preparing photographic color images in the presence of a color coupler. It relates also to photographic material containing such color couplers and to photographic images obtained according to this method.

The method for the preparation of photographic color images by color development comprises the development of a silver salt image of an exposed photographic material, in the presence of a color coupler, by means of a developer containing an aromatic amine as a developing substance. The color coupler can either be incorporated into the developing solution or provided in the photographic material. During the development, oxidation products of the amino developer are formed. These oxidation products and said color coupler couple to produce a color image in the area where the silver salt image has been developed.

The up to date methods for color photography are based on the subtractive color principle according to which differently sensitized silver halide emulsions are applied as superimposed layers, each layer containing the color coupler which, by development in a developer comprising an aromatic amine developing substance, produces the subtractive yellow-, cyanor magenta color images.

For preventing the difiusion of these color couplers from their original layer to an adjacent layer in case a photographic multilayer material is used, a substituent such as a long aliphatic chain comprising 5 to 20 C-atoms is usually introduced into the molecular structure of these color couplers. In order to facilitate the incorporation of such a color coupler into a photographic layer it is often desirable to introduce moreover a solubilizing group into the molecule.

It is known to use acyl acetarylides as color couplers for yellow. The aroyl acetarylides sulfonated in the arylide group, can be obtained by the condensation of an aroyl acetic acid ester with a compound corresponding to the general formula:

' NH -ArylSO F (wherein the aryl nucleus can contain a radical to prevent the migration into another emulsion layer) whcreafter the resulted compound is hydrolized in an alkaline medium to convert the sulfonyl group into a sulfonate group (our British Patent 808,276).

As a further possibility to synthesize this type of molecule, the aroyl acetic acid ester can contain a nitro group which is reduced after the condensaiton to an amino group. In this amino group, a non-migratory making group will beintroduced according to a known method e.g. by condensation with a long aliphatic chain comprising carboxylic acid chlorides or sulfonyl chlorides.

However, it has further been noticed (our British Patent Specification 808,276, prep. 6, ex. V) that when p-myristoyl amino-m-nitrobenzene sulfonylfluoride is catalytically reduced to p-myristoyl-amino-m-amino-benzene sulfonylfluoride, ring-closure of this latter compound also occurs, leading to a tridecyl benzimidazole derivative. Similar modification is noticed while condensing with benzoyl acetic acid ester whereby a pure color coupler cannot be prepared in this Way.

A new method has been found whereby color couplers, which contain a group making the molecule non-migratory and a solubilizing group in the arylide nucleus, can be prepared by condensing aromatic amino sulfonylfluorides containing such a non-migratory making group with diketene or acyl acetic acid esters.

The reaction can be illustrated by the following formula:

wherein R represents a member selected from the group consisting of an aromatic radical, such as phenyl, a substituted aromatic radical such as p-methoxyphenyl; an heterocyclic radical such as Ot-flllyl, and 3-pyridyl;

R represents a lower alkyl radical, such as CH or Ar represents an aromatic monocyclic radical of the henzene series; Z represents a member selected from the group consisting of O, -S, 40

D represents an aliphatic radical comprising a linear chain of at least 5 and at most 20 C-atoms.

The non-migratory aromatic amino sulfonylfluorides used in the preparation of complexes according to the present invention do not show the above-mentioned disadvantage of ring-closure and moreover they are very well appropriate for condensation with a number of B-ketone esters, whereby the prepared color couplers are obtained in a very pure state with a high yield.

Moreover, a greater number of said color couplers can be obtained since a high number of fl-ketone esters, without a non-migratory making group, can more easily be prepared than the corresponding non-migratory fl-ketone esters, whereas moreover non-migratory aromatic amino sulfonylfluorides can be prepared without great ditficulty.

The condensation products prepared according tothe present invention are obtained as white crystalline compounds with a high yield. Said fiuorosulfonyl derivatives are easy to purify by recrystallization and remain unchanged during storage.

According to a first embodiment of the present invention it is possible, starting from the stored sulfotluoride, to saponify same in an alkaline solution; then after setting to a suitable pH, said product can be added to the emulsion.

According to a second embodiment it is also possible to use the separated and sulfonated product as starting material. a

In the first case the condensation products obtained are very quickly saponified by dissolving '1 mol of sulfonyl- In the second case the sulfonyl derivatives can be saponified in an acetone medium with an aqueous solution of sodium hydroxide or potassium hydroxide. According to this method the color couplers can be separated in a pure state as a white crystalline compound in a high yield.

For adding the color coupler thus obtained to the emulsion it suffices to dissolve the color coupler previously in water; the pH value is adjusted according to the case.

The following preparations illustrate the present invention without limiting, however, the scope thereto.

(1) Preparation of a-Furoyl-(2-Cetylmercapto-S-Sulfo)- Acetanilide-Sodium Salt (A): PREPARATION OF a-FUROYL-(2-CETYLMERCAPTO- 5-FLUOROSULFONYL)-ACETANILIDE 21.5 g. of Z-(cetylmercapto-S-fluorosulfonyl) aniline (prepared according to the Belgian Patent 587,525) and 9.1 g. of a-furoyl acetic acid ethyl ester (prepared according to J. Am. Chem. Soc. 73 p. 5857 1951) are refluxed with 100 cmfi of anhydrous xylene. For 2 h. a mixture of xylene and ethanol is distilled off. The remaining xylene is distilled off in a vacuum.

The remaining residue is mixed with acetonitrile and this mixture is cooled to C. The precipitate formed is recrystallized from n-hexane whereby 18 g. of white crystals are obtained. Melting point: 83 C.

(B) PREPARATION OF a-FUROYL- 2CETYLMERCAPTO- -SULFO)-ACETANILIDE s DIUM SALT Whilst stirring, 11.7 g. of said sulfofluoride derivative are refluxed together with 100 cm. of acetone. After adding 12 cm. of sodium hydroxide 5 N the mixture is further refluxed for 30 min. The reaction mixture is acidified with acetic acid and whilst stirring it is cooled to room temperature. The precipitate formed is filtrated oh and recrystallized from methanol whereby 7 g. of a color coupler are obtained as a white powder.

(2) Preparation of ot-Furoyl-(2-Cetylsulfonyl-5-Sulfo)- Acetanilide-Sodium Salt (A) PREPARATION OF a-FUROYL-(2-CETYLSULFONYL- 5-FLUOROSULFONYL) ACETANILIDE 9.26 g'. of 2-cetylsulfonyl-5-fluor0sulfonyl aniline (prepared according to the German Patent Application G 28,816 filed January 15, 1960) and 3.64 g. of a-furoyl acetic acid ethyl ester are refluxed with 50 cm. of anhydrous xylene. Within the course of 2 h. xylene and splitted ofl ethanol are gradually distilled off to a total volume of 40 cm. then n-hexane is added to the reaction mixture. After cooling to room temperature the formed precipitate is filtered off and recrystallized from n-hexane. Melting point: 72 C.

(B) PREPARATION OF a-FUROYL-(2-CETYLSULFONYL- 5-SULFO)-ACETANILIDE SODIUM SALT Whilst stirring, 5.99 g. of said sulfofluoride derivative are refluxed together with 60 cm. of acetone. After adding 6 cm. of sodium hydroxide 5 N this reaction mixture is still further refluxed for 1 h. whilst stirring. Next, the reaction mixture is acidified with acetic acid and then cooled to room temperature whilst stirring. The precipitate formed is recrystallized from acetic acid and a white crystalline sodium salt is obtained.

(3) Preparation of Isa-N icotinoyl- (3 -S ul )04 -C etylm ercapto) -A cetanilide Sodium Salt (A) PREPARATION OF ISO-NICOTINOYL-(3-FLUORO- SULFONYL-at'CETYLMERCAITO) ACETANILIDE 12.9 g. of (3-fluorosulfonyl 4- cetylmercapto) aniline (prepared according to the German Patent Application G 28,816, filed January 15, 1960) and 5.4 g. of isonicotinoyl acetic acid methyl ester (prepared according to J. Am. Chem. Soc. 65 p. 2460, 1943) are refluxed with 120 cm. of anhydrous xylene. For 1 h. a mixture of xylene and methanol, which has been splitted off, is distilled off to a volume of 50 cm. The xylene solution is removed under reduced pressure and then treated with n-hexane.

After recrystallizing the formed precipitate from a mixture of n-hexane/acetone, 8 g. of a white crystalline product are obtained. Melting point: 108 C.

(B) PREPARATION OF ISO-NICOTINOYL-(B-SULFO-at- (JETYLMERCAPTO -ACETANILIDE-SODIUM SALT 5.78 g. of said sulfonylfluoride derivative are refluxed with 40 cm. of acetone. Whilst stirring this mixture is refluxed fro 30 min. after adding 6 cm. of sodium hydroxide 5 N. The reaction mixture is acidified with acetic acid and then cooled to room temperature whilst stirring. The formed precipitate is filtrated oli and recrystallized from dimethyl formamide. In this way 4.5 g. of a white product are obtained.

(4) Preparation of p-Methoxybenzoyl-(Z-Cetylmercapto- 5-Sulf0) -Acetanilide Sodium Salt (A) PREPARATION OF PMETHOXY BENZOYL-(2-CET- YLMERCAPTO-5-FLUOROSULFONYL)-ACETANILIDE 34.5 g. of 2'cetylmercapto-S-fluorosulfonyl aniline (prepared according to the Belgian Patent 587,525) and 17.7 g.

of p-methoxy benzoyl acetic acid ethyl ester are refluxed with 150 cm. of anhydrous xylene. Within the course of 2 h. a mixture of 120 cm. of xylene and ethanol is distilled off. After cooling, the reaction mixture is treated with cm. of hexane. The formed precipitate is filtrated, washed with n-hexane and recrystallized from ethanol. Melting point: C.

(B) PREPARATION OF P-METHOXYBENZOYL-(2-CE'1YL- DIERCAPTO-5-SULFO)ACETANILIDE SODIUM SALT 21.5 g. of said sulfofiuoride derivative are refluxed with 150 cm. of acetone. Whilst stirring this mixture is refluxed for 30 min. after adding 21 cm. of sodium hydroxide 5 N. After acidifying with acetic acid the reaction mixture is cooled whilst stirring. The formed precipitate is filtrated off and washed with a little water.

After recrystallization from methanol 17 g. of a White product are obtained.

(5) Preparation of Benzoyl-(Z-Cetylmercapto-S-Sulfo)- Acetanilide Potassium Salt (A) PREPARATION OF BENZOYL-(2-CETYLMERCAPTO- 5-FLUOROSULFONYL) -ACETANILI DE 43.1 g. of Z-cetylmercapto-S-fluorosulfonyl aniline (prepared according to the Belgian Patent 587,525) and 19.2 g. of benzoyl acetic acid ethyl ester are refluxed with 150 cm. of anhydrous xylene. For 1 h., cm. of a mixture of xylene and ethanol is distilled off. After cooling the reaction mixture to 50 C., the reaction product is treated with 500 cm. of n-hexane and this mixture is then cooled to room temperature. The formed precipitate is filtrated off, washed with n-hexane and recrystallized from isopropanol. Melting point: 95-96 C.

(B) PREPARATION OF BENZOYL-(Q-CETYLMERCAPTO- 5-SULFO)-ACETANILIDE POTASSIUM SAUL 28.9 g. of said sulfonyl fluoride derivative are refluxed with cm. of acetone. Whilst stirring, this mixture is further refluxed for 1 h. after adding 30 cm. of potassium hydroxide 5 N. After acidifying with acetic acid the reaction mixture is cooled to room temperature. The formed precipitate is filtrated off, washed with a little water and recrystallized from iso-propanol, whereby a white product is obtained.

(6) Preparation of Acetyl-(Z-Cetylsulfonyl-S-Sulfo)- Acetanilide Sodium Salt (A) PREPARATION OF ACETYL-(2-CETYLSULFONYL- S-FLUOROSULFONYL) -ACETANILIDE 46.3 g. of Z-cetylsulfonyl-S-fluorosulfonyl aniline (prepared according to the German Patent Application G 28,816, filed January 15, 1960) are brought into 200 cm. of anhydrous toluene and this mixture is stirred at 30 C. Some droplets of triethylamine are added and 8.4 g. of diketene are then dropwise added for 10 min. After stirring for 45 min. at 60-70 C., the reaction mixture is cooled to room temperature. Next, 200 cm. of

n-hexane are added to the reaction mixture and then the reaction mixture is cooled to C. The formed precipitate is filtrated off, washed with n-hexane and recrystallized from a mixture of ethanol and water. Melting point: 90-92" C.

(B) PREPARATION OF ACETYL-(2-CETYLSULFONYL-5- SULFO) ACEIANILIDE SODIUM SALT 19.1 g. of said sulfonylfluoride derivative are refluxed with 150 cm. of acetone. Then 20 cm. of sodium hydroxide N are added to this solution and Whilst stirring the reaction mixture is still further refluxed for 1 h. After acidifying with acetic acid the reaction mixture is cooled to room temperature whilst stirring. The formed white precipitate is filtrated off, washed with water and recrystallized from acetonitrile.

(7) Preparation of Benzoyl-(Z-Cetylsulfonyl-S-Sulfo)- Acetanilide Sodium Salt (A) PREPARATION OF BENZOY'L-(2-CETYLSULFONYL- 5 FLUORO SULFONYL) ACETANILIDE 46.3 g. of 2-cetylsulfonyl-S-fluorosulfonyl aniline (prepared according to the German Patent Application G 28,816, filed January 15, 1960) and 19.2 g. of benzoyl acetic acid ethyl ester are refluxed with 150 cm. of anhydrous xylene. For 2 h., 100 cm. of a mixture of xylene and ethanol are distilled ofr. The oily residue is treated with 300 cm. of methanol and then cooled to 0 C. The formed white precipitate is filtrated ofr, washed with methanol and recrystallized from ethanol. In this way 30 g. of a White crystalline product are obtained. Melting point: 117 C.

(B) PREPARATION OF BENOZYIJ-(2-CETYLSULFONYL-5- SULFO)-ACETANILIDE SODIUM SALT 6.09 g. of said sulfonylfluoride derivative are refluxed with 40 cm. of acetone. Next, 6 cm. of sodium hydroxide 5 N are added to this solution and then the reaction mixture is refluxed for 1 /2 h. whilst stirring. Next, the reaction mixture is acidified with acetic acid and cooled to room temperature. The formed precipitate is filtrated off and washed with a little water. After drying, 6 g. of a white product are obtained which is recrystallized from methanol.

(8) Preparation of Benzoyl-(2-Cetyloxy-5-Sulfo)- Acetanilide Sodium Salt (A) PREPARATION OF BENOZYL-(2-CETYLOXY-5-FLUO- R0 SULFONYL) ACETANILIDE A mixture of 6.33 g. of 2-cetyloxy-S-fluorosulfonyl aniline (prepared according to the Belgian Patent Application No. 39,775 filed May 18, 1960) and 2.88 g. of benzoyl acetic acid ethyl ester are refluxed in 30 cm. of anhydrous xylene. For 2 h. a mixture of xylene and splitted off ethanol is distilled 01f and then the remaining xylene is removed in vacuo. During the evaporation the product is precipitated. After treatment with hexane the white precipitate is filtrated off, Washed with hexane and recrystallized from ethanol. Melting point: 103-104 C.

(13) PREPARATION OF BENz0YL-(2-cE1TYLOXY-5- SULFm-AcETANILIDE SODIUM SALT 4.48 g. of said sulfonylfluoride derivative are refluxed with 30 cm. of acetone whilst stirring. After adding 6 4.8 cm. of sodium hydroxide 5 N, the reaction mixture is still further refluxed for 45 min. whilst stirring. Next, the reaction mixture is acidified with acetic acid and then cooled whilst stirring. A white precipitate is formed which is recrystallized from methanol, whereby 4 g. of a White crystalline product are obtained.

(9) Preparation of Benzoyl-[Z-(N-Methyl Cetyl) Amino- 5-Fluor0sulf0nyl]Acetanilide Sodium Salt (A) PREPARATION OF 1BENZOYL-[2-(N-METHYL CE- TYL) AMINO5-FLUOROSULFONYL]ACETANILIDE 6.42 g. of Z-(N-methyl cetyl)amino-5-fluorosulfonylaniline (prepared according to the Belgian Patent Application No. 39,775, filed May 18, 1960) and 2.88 g. of benzoyl acetic acid ethyl ester are refluxed with 30 cm. of anhydrous xylene. A mixture of xylene and splitted ofl ethanol are distilled off for 2 h., then the remaining xylene is removed in vacuo. After treatment with hexane and cooling to 0 C., the formed precipitate is filtrated ofi? and recrystallized from n-hexane. In this way 6 g. of a fine white crystalline product are obtained. Melting point: 73 C.

(B) PREPARATION OF BENz0YL-[2-(N-METHYL CE- TYL-)-AMIN05-sULFoJACETANILIDE SODIUM sALT 5.74 g. of said sulfonylfluoride derivative are refluxed with 40 cm. of acetone Whilst stirring. Then, 6 cm. of sodium hydroxide 5 N are added to the resulted solution and this solution is still further refluxed for 1 h. The formed precipitate is recrystallized from methanol.

Yield: 4 g.

We claim: Sulfonated acetarylides having the formula SO Me ROOCHrC ONH-Ar wherein:

and D is alkyl of from 5 to 20 carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS Lacey et al. July 26, 1955 OTHER REFERENCES Perekalin et al. I. of Gen. Chem., U.S.S.R, vol. 21, pages 2219-4, 1951.

Perekalin et al. Usepekhi Khimi, vol. 25, pages 1351- 72, 1956.

Noller Chemistry of Organic Compounds, 2nd Ed., pp. 470-71: 288-9, 1957. 

